Dyeing regenerated cellulose rayon



Patented July 26, 193

UNITED STATES PATENT OFFICE RAIN-ALB BRIG'I TMAN, or MANCHESTER, ENGLAND, ASSIGNOR TO IMPERIAL CHEM- ICAL INDUSTRIES LIMITED, or LONDON, ENGLAND DYEING REGENERATED CELLULOSE RAYON No Drawing. Application filed July 27, 1929, Serial No. 381,693, and in Great Britain September 12, 1928.

By this invention regenerated cellulose rayon, such as viscose rayon 1s dyed 1n level shades with the dyestuffs obtained by diazo-' tizing (or tetrazotizing) and combining a.

t-aminoor 4: 4-diamino diphenylamine with one or two molecular proportions respectively of an aminonaphtholsulphonic acid, or a derivative thereof, or, in the case of the tetrazo body,- combining it with one molecular proportion of anaminonaphtholsul phonic acid or a derivative thereof, for instance, the phenol and benzoyl N-substituted derivatives, and one molecular proportion of another component, but when sulphonic acids of 4-aminodiphenylamine are employed we use only monosulphonic acids of aminonaphthols or derivatives thereof as coupling components in order to ensure a sufficient aflinity of the formed dyestufl' for regenerated cellulose rayon. These dyestuffs may be represented by the general formula wherein R represents hydrogen, an alkoxy or a sulphonic group, R represents the coupled residue of an aminonaphthol sulphonic acid 'and X represents hydrogen or the group N=NR wherein R represents the coupled residue of an azo dye coupling component.

Other generic formulae which can be used to represent the dyestuffs of my invention are p as follows a naphthol, salicylic acid or phenyleriediamine wherein R and R have their former significanoe; and

wherein R represents an aminonaphthol sulphonic acid such as 2-amino-8-naphthol sulphonic acid, 2-phnylamino-5-naphthol sulphonic acid or 1-amino-8-naphthol sulphonic acid;

These dyes are dark powders dissolving in water to blue or violet solutions which are substantially unchanged by addition of dilute alkali and afford a precipitate on the. addition of dilute acid. By the use of these dyes relatively level shades on regenerated cellulose rayon may be obtained and according to the aminonaphthol sulphonic acid employed various blue and violet shades result. 7 7

Some of these dyestuffs are already known and have been described for the dyeing of unmordanted cot-ton, but in view of the very uneven dyeings'whiehthe usual direct blue cotton dyestuffs give on viscose rayon, it could not have been forseen that the above dyestuffs would give such excellent results and my invention constitutes a notable advance in the art of dyeing regeneratedcellulose rayon. I

The following example illustrates the invention without limiting it, the parts being by weight.

ExampZe.The dyebath is made up from 3000 parts of water, 20 parts of Glaubers salt, 3 parts of soap and 1 part of the dyestufi' obtained bycombining 1 molecular part of tetrazotized 4:4-diaminodiphenylamine with 2 molecular parts ,of l-amino-S-naphrinsed and tholl-sulphonic acid. parts of the regenerated cellulose rayon are enteredinto thebath :7 warm and the bath is then raised nearly to the boiling point and the dyeing is carried on for about hour. The fabric is then removed, dried. Alternatively the rayon' may be entered into the bath nearly at the boiling point and the bath allowed to cool gradually during the dyeing. Moreover, there may also be added to the dyebath other salts or dyeing assistants such as borax or sodium'carbonate. The rayon is dyed an even light blue shade.

The examples shown inthe following table further illustrate the invention, the' aminonaphthol sulphonic acids being coupled in all cases in alkaline solution:

The 1: l diamino 2 methoxydiphenylaminewhich is referred to may be obtained by the condensation of p-nitrochlorobenzene with p-nitro-o-anisidine and reducton of the resulting dinitro compound (melting point of latter l lO-lll (1.). The 4: 4-diamino-2- methoxydiphenylamine can be coupled with the azo dye components of the tableand the resulting dyes give satisfactory results in dyeing regenerated cellulose.

blue solution which remalns substantially unchanged on the addition of dilute alkali and which yields a bluish precipitate on the addition of dilute acid.

2. Regenerated cellulose rayon material dyed in relatively level blue shades by means of a dyestufl which in the form of its free acid has the probable formula on NH: N=N-SO:H scan NH 3. Regenerated cellulose rayon material Coupled with- Shade on vis- 1. 4-an1inodipheny1amine 2. Do

sulphonic acid.

diamin phonic acid.

diamine.

2 mols. of 2-amino-8-naphthol-fi-sulphonic acid 1 mol. of salicylic acid and 1 mol. of 2-phenylamino-5-naphthol-7-sulphonic aci(l 1 mol. of salicylic acid and 1 mol. of 2-benzoylaminO-Smaphthol-fi-Sulplionic acid 1/ mol. of l-amino-S-naphthol 3 fi-disulphonic acid e. 1 mol. of l-amino-B-naplithol 3 fi-disulphonic acid and 1 mol. of m-phenylenc cose rayon 2-phenylamino-5-naphthol-7-su1plionic acid Violet. 1-amino-8-naphth0l-2 4-disulphonic acids. Sky-blue. l-amino-8-naphthol-3 6-disulphonic acid Royal blue. 1 mol. of l-amino-B-naphtliol-Z 4-disulphonic acid and 1 mol. of B naphthol. Rcddish-blue.

1 mol. of l-amino-B-naphthol 3 fi-disulphonic acid and 1 mol. of l-naphthol-i- Royal blue.

Reddish-bluc.

Navy blue.

and 1- mol. ofgn-phenylene Do.

Blue-black.

What I claim and desire to secure by Letters Patent is:

l. The process of dyeing regenerated cellulose rayon material blue and relatively level shades which comprises the application to the material of a dyestuff which in the form of its free acid has the probableformula.

OH NH! which dyestufi dissolves water giving a having an even dyed by .means of a dyestufl having the probable formula pi i H II}:

wherein R -represents hydrogen, an alkoxy or a sulphonic group and R represents the coupled residue of phonic acid, the said dyed rayon material level blue to violet shade.

4. Regenerated cellulose rayon material dyed by means of a dyestuff having the probable formula the said dyed rayon material having an even level royal-blue shade.

5. Regenerated cellulose rayon material an aminonaphthol sulin Au 1,ses,ese

dyed by mean's of a dyestufi' having the probable formula the said dyed rayon-material having an even level reddish-blue shade. r

6. Regenerated cellulose rayon material dyed by means of a dyestufi' having the probable formula wherein R represents hydrogen, an alkoxy or sulphonic group, R represents the coupled residue of an aminonaphthol sulphonic acid and X represents hydrogen or the group -N=NR wherein R represents the coupled residue of an azo dye couplingcomponent. v

7; Regenerated cellulose rayon material dyed by means of a dyestuflt' having the robable formula wherein R represents hy'drogeman alkoxy or sulphonic group, R, represents an aminonaphth'ol sulphonic acid and R represents the coupled residue of, an aminonaphthol sul-' phonic acid, a naphthol, salicylic acid or phenylenediamine.

8. Regenerate-d cellulosev rayon material I dyed by means of a dyestufi' having the probe able formula wherein R represents hydrogen, an alkoxy or a sulphonic group, R represents the coupled residue of a 2-amino-8-naphtholsulphonic acid, a 2-phenylamino-5-na hthol sulphonic acid or a 1-amino-8-nap thol sulphonicacid and X represents hydrogen or the group N=NR wherein R, repredyed by means of a sents the coupled residue pling component.

9. Regenerated cellulose of an azo dye courayon material dyestufl' having the probable form'u la v t wherein R represents hydrogen, an alkoxy or a sulphonic group and R-{represents the coupled residue of a 2-amino-8-naphthol sulphonic acid, a 2-phenylamino -na hthol sulphonic acid or a 1-amino-8-nap tho'l sulphonic acid, the said dyed rayonmaterial having an even level blue to violetshade.

10. Regenerated cellulose rayon material dyed by means of a dyestufi having the probable formula v wherein R represents hydrogen, an alkoxy or a' sulphonic group, R represents the coupled residue of a 2-amino-8 naphthol sulphonic acid, a 2-phenylamino-5-naphthol sulphonic acid or a'1-amino-8-naphthol sul- 8.

phonic acid, and R, represents the coupled residue of an aminonaphthol sulphonic acid,

a naphtliol, salicylic acid or phenylenediamine.

ll. Regenerated cellulose rayon material dyed by means of a dyestufi having the probable formula wherein R represents hydrogen or, an alkoxy or sulphonic group, R represents the coupled residue of an aminonaphthol su lphonic acid and X represents hydrogen or the group N=NR wherein R represents the coupled residue of an azo dye coupling com- 7 ponent. i

13. In the dyeing of regenerated cellulose rayon material blue to violet and in relatively .level shades, the process which comprises applying to the .said regenerated materialdyes of the general formula R p I wherein R represents hydrogen, an alkoxy or a sulphonic group, R represents an amino napthol sulphonic acid andR, represents prises applying tot-he said regenerated mateor a sulphonic group and R represents the the coupled residue of an aminonaphthol sulphonic acid, a na-phthol, salicylic acid or phenylenediamine.

14. In the dyeing of regenerated cellulose 5 rayon material blue to violet and in relative- 1y level shades, the process which comprises applying to the said regenerated material dyes of the general formula wherein R represents hydrogen, an alkoxy or a sulphonicgroup, R represents the cou- 5 pled residue of a 2-amino-8-naphthol sul-' phonic acid, a 2-phenylamino-5-naphthol sulphonic acid or a l-amino-S-naphthol sul- P phonic acid and X represents hydrogen or" the group -N=NR wherein R repre- 0 sents the coupled residue of an azo dye coupling component.

15. In the dyeing of regenerated cellulose rayon material blue to violet and in relativelylevel shades, the process which comrial dyes of the general formula wherein R represents hydrogen, an alkoxy or a sulphonic group, R represents the coupled residueof a 2-amino-8-naphthol sulphonic acid, 2-phenylamino-5-naphthol sulphonic acid or a l-amino-S-naphthol sulphonic acid, and R re resents the coupled residue of an aminonap ithol sulphonic acid anaphthol, salicylic acid or phenylenedi amme.

17. In the dyeing of regenerated cellulose rayon material blue to violet and in relatively level shades, the process which comprises applying to the said regenerated material 6O dyes of the general formula y wherein R represents hydrogen, an alkoxy residue of a 2-amino-8-naphthol sulcoupled acid, a 2-phenylamino-5-naphthol phonlc sulphonic acid or a 1-amino-8-naphthol sulphonic acid.

18. In the dyeing of regenerated cellulose rayon material blue to violet andin relatively level shades, the process which comprises applying to the said regenerated material dyes of the general formula wherein R represents hydrogen, an alkoxy or a sulphonic group and R represents the coupled residue of an aminonaphthol sulhonic acid.

19. In the dyeing of regenerated cellulose rayon material blue to violet and in relatively level shades, the process which comprises applying to the said regenerated material dyes of the general formula H O NH: I

In testimony whereof I aflix my signature.

RAINALD BRIGHTMAN. 

